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Electronic Theses and Dissertations

2018

Chemistry and Biochemistry

Chemistry

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Fuel Specific Emissions Trends For In-Use Medium And Heavy-Duty Vehicle Fleets In California, Molly J. Haugen Aug 2018

Fuel Specific Emissions Trends For In-Use Medium And Heavy-Duty Vehicle Fleets In California, Molly J. Haugen

Electronic Theses and Dissertations

New heavy-duty vehicle regulations have caused significant reductions in hazardous air pollutants, such as particulate matter (PM) and nitrogen oxides (NOx), due to better engine management and utilization of advanced after-treatment systems. The University of Denver has collected data for gaseous and PM emission measurements from on-road heavy-duty vehicles (HDVs). The On-Road Heavy-Duty Vehicle Emissions Measurement System (OHMS) collected fuel specific emission information on individual HDVs of in-use fleets at two California locations in the spring of 2013, 2015 and 2017. These complimentary fleets, studied over multiple years, produced 7,075 measurements of gaseous and particle emission data providing …


Selective Carbon-Carbon Bond Formation Promoted By Divalent Samarium Reagents, Christopher David-James Aretz Jan 2018

Selective Carbon-Carbon Bond Formation Promoted By Divalent Samarium Reagents, Christopher David-James Aretz

Electronic Theses and Dissertations

Three efficient methods for synthesis of five membered carbocycles, a highly understudied product motif in samarium(II) chemistry, were explored and optimized. These methods utilized simple starting materials to generate linear substrates with functional groups that are reactive towards samarium(II) iodide. The three methods explored were the Reformatsky-aldol, Reformatsky-alkylation, and pinacol cyclizations. The critical discovery for efficient formation of the Reformatsky-aldol and pinacol carbocycles products was the use of lithium bromide. This addition of lithium bromide facilitates easy in situ formation of samarium(II) bromide. The Reformatsky-alkylation cyclization was a newly realized reaction employing samarium enolates. Two of the three methods, the …


Photochemistry Of Polycyclic Aromatic Hydrocarbons With Environmentally Relevant Metals, John P. Haynes Jan 2018

Photochemistry Of Polycyclic Aromatic Hydrocarbons With Environmentally Relevant Metals, John P. Haynes

Electronic Theses and Dissertations

The details of the work presented in this dissertation focus on simulated reactions in the atmosphere and water systems between persistent aromatic compounds and varying species of metals with an emphasis on iron. Bulk water suspensions of a standard soil and polycyclic aromatic hydrocarbons (PAH) were analyzed for soluble iron by inductively-coupled plasma mass spectroscopy (ICP-MS) following a 16 hour reaction period using simulated sunlight. Significant increases in soluble iron were only seen with 2-3 ring linear PAH and carboxylic acids.

A two-stage study was conducted to investigate the potential for and possible mechanisms involving the photo-oxidation of PAH into …


The Investigation Of Lactoferrin Nitration: Quantification, Function, And Inhibition, Amani Yahya Alhalwani Jan 2018

The Investigation Of Lactoferrin Nitration: Quantification, Function, And Inhibition, Amani Yahya Alhalwani

Electronic Theses and Dissertations

Lactoferrin (LF) is an iron-binding glycoprotein of molecular mass ca. 80 kDa that is predominantly found in mammalian body fluids. Lactoferrin is a multifunctional protein that has a wide range of properties such as antibacterial, antiviral, anti-inflammatory, and anti-allergic functions. Tyrosine residues in the protein play a part in many lactoferrin functions. Protein tyrosine nitration modification represents an oxidative and nitrosative stress process which can be caused by the exposure of proteins to oxidants from air pollution or disease. Understanding the way nitrated lactoferrin interacts with the biochemical environment of the body is thus important to the broader goal of …


Brønsted Acid Catalyzed Carbon-Carbon Bond Forming Reactions, Jiangyue Miao Jan 2018

Brønsted Acid Catalyzed Carbon-Carbon Bond Forming Reactions, Jiangyue Miao

Electronic Theses and Dissertations

The focus of this research project lies in the development of new methodology in the field of Brønsted acid catalysis enabling rapid synthesis of medicinally relevant compounds. It is foreseen that small molecule sulfonic acids evaluated in this research project will unveil new asymmetric carbon carbon bond forming reactions between substrates hitherto unexplored with Brønsted acid catalysis. It has been established that strong Brønsted acids, such as phosphoric acids, are capable of mediating highly selective transformations operating through unique mechanistic manifolds.

Specific focus for the sulfonic acid catalysts was geared towards asymmetric coupling reactions with synthetically useful precursors such as …